Process for anodizing aluminum and its alloys

ABSTRACT

AN ANODIZING SYSTEM USES BOTH POSITIVE AND NEGATIVE CURRENT PULSES. SUCH PULSES ARE ADJUSTABLE TO ACHIEVE DIFFERENT ADJUSTED VALUES OF POSITIVE AND NEGATIVE CURRENTS. THESE VALUES ARE SENSED AND USED TO MAINTAIN AUTOMATICALLY SUCH VALUES. THE RATIO OF NEGATIVE CURRENT TO POSITIVE CURRENT IS PREFERABLY GREATER THAN 3% FOR THE PRODUCTION OF RELATIVELY THICK, DYEABLE, HARD ANODIZED COATINGS AND CONVENTIONAL (NORMAL) ANODIC COATINGS OF LIGHT SHADES OF INTEGRAL COLORS USING A SIMPLE SULFURIC ACID BATH WHICH MAY BE MAINTAINED AT RELATIVELY HIGH TEMPERATURES. CURRENT MAY BE APPLIED AT NEARLY FULL CURRENT DENSITY INITIALLY WITHOUT BURNING. IN SOME CASES, ADDITIONAL MEANS MAY BE PROVIDED TO INCREASE THE THROWING POWER BY ELIMINATING THE NEGATIVE CURRENT AND USING MEANS SUCH AS CAPACITORS OR INDUCTORS TO PROLONG THE DECAY OF THE POSITIVE PULSES, PREFERABLY SUCH THAT THE THEN COMPOSITE POSITIVE PULSES ARE MAINTAINED ABOVE A ZERO VALUE. THESE COMPOSITE POSITIVE PULSES ARE MAINTAINED IN A RATIO AND WAVE SHAPE WHICH YIELDS BOTH GOOD &#34;THROWING&#34; POWER AND HIGH QUALITY, EVEN COATINGS, AND PRODUCES THE ANODIC COATINGS AT RELATIVELY HIGH CURRENT DENSITIES.

Aug. 3, 1971 F, s, NEWMAN ErAL 3,597,339

PROCESS FOR ANODIZING ALUMINUM AND ITS ALLOYS Filed Sept. 9, 1968 3 Sheets-:Sheet 1 2/4 0/ (a) 20? 2&4

. Var/465 466055 72m/ (by j' Var/465 Z/Z.

gg El@ 6. e y l A NUE/ff V5 Aug. 3, 1971 F, s, NEWMAN ETAL 3,597,339

PROCESS FOR ANODIZING ALUMINUM AND ITS ALLOYS Filed Sept. 9, 1968 3 Sheets-Sheet 2 Q 5 506265701@ @i4/v7? PROCESS FOR ANODIZING ALUMINUM AND ITS ALLOYS Filed Sept. 9, 1968 Allg. 3, 1971 F, s, NEWMAN ETAL 3 Sheets-Sheet I5 JOHN 7." HAEM/IA/ 3,597,339 PRCESS FR ANUDllZlNG ALUMHNUM AND i'lf ALILYS Frederick d. Newman, Canoga Park, llloliin E. Thorne,

Hidden Hills, and lohn li. Hartman, Reseda, Calif.,

assignors to Scionies of California, llnc.

liiled Sept. 9, 1968, Ser. No. 758,258 lint. Cl. C23b 9/02;Btl1k 3/(10 US. Ci. 20d-58 l2 Claims ABSTRACT @F THE DISCLOSURE An anodizing system uses both positive and negative current pulses. Such pulses are adjustable to achieve different adjusted values of positive and negative currents. These values are sensed and used to maintain automatically such values. The ratio of negative current to positive current is preferably greater than 3% for the production of relatively thick, dyeable, hard anodized coatings and conventional (normal) anodic coatings of light shades of integral colors using a simple sulfuric acid bath which may be maintained at relatively high ternperatures. Current may be applied at nearly full current density initially without burning, In some cases, additional means may be provided to increase the throwing power by eliminating the negative current and using means such as capacitors or inductors to prolong the decay of the positive pulses, preferably such that the then composite positive pulses are maintained above a zero value. These composite positive pulses are maintained in a ratio and wave shape which yields both good throwing power and high quality, even coatings, and produces the anodic coatings at relatively high current densities.

The present invention relates to improved means and techniques which are particularly useful in the production of anodized coatings.

A specific object of this present invention is to provide a system where the effective current density may be adjusted by adjusting input voltage while the average current density is maintained at a predetermined level.

Another specific object of the present invention is to provide a system of this character which advantageously uses a simple bath mixture, but is not dependent on such simple bath.

Another specific object of the present invention is to provide a system of this character that uses negative current to great advantage.

Another specific object of the present invention is to r provide a power supply for a system of this character which sequentially supplies positive and negative currents to a load.

Another specific object of the present invention is to provide a power supply for a system of this character which is capable of supplying a large and adjustable amount of negative current for the production of new and improved results.

Another specific object of the present invention is to provide a power supply for a system of this character which is adjustable to supply dilferent amounts of positive and negative currents and which when so adjusted functions to maintain automatically the amounts and ratios so preadjusted.

Another specific object of the present invention is to provide new means and techniques which advance the .hard and conventional anodizing arts.

Another specific object of the present invention is to 3,597,339 Patented Aug.. 3, i971 provide a system of this character in which satisfactory hard and conventional anodizing may be accomplished at higher bath temperatures than now known to the art.

Another specilic object of the present invention is to provide new means and techniques having the advantage that hard anodized objects produced thereby are remarkably light colored and receptive to dye stuffs for coloring purposes.

Another specific object of the present invention is to provide new means and techniques that permit the use of high current densities in the bath for greater speed of processing.

Another specific object of the present invention is to provide new means and techniques that permit the application of full, or nearly full, current density at the start of the anodizing cycle Without adversely affecting the part being anodized.

Another specific object of the present invention is to provide a system which will simplify the anodizing process enabling operators of lesser skill than now practical to perform the anodizing.

Another specific object of the present invention is to provide a system of this character which uses at least 3% and preferably larger percentages of negative current, such percentage being an expression of the ratio of negative current ow during the negative half cycle of an A.C. wave to the average positive current ow during the positive half cycle of the same A C. wave.

Another specific object of the present invention is to provide a system of this character in `which there is less tendency for the parts being anodized to burn thereby allowing the use of higher current densities, shorter processing times, the production of thicker coats of higher dielectric strength, and immediate start up at the desired current levels.

Another specic object of the present invention is to provide an improved system of this character in which the bath may consist only of a solution of water and sulfuric acid, although more complex baths may be used if desired.

Another specific object of this invention is to provide a system which will coat copper bearing alloys, and other hard to anodize alloys, to greater thicknesses in shorter times than heretofore practical without burning or softening the coat.

Another specic object of this invention is to provide a system which will build an anodic coat with improved abrasion resistant qualities.

Another specific object of this invention is to provide a system which contains means of varying operating parameters so that the proper parameters can be selected and automatically achieve and optimize the particular characteristic of the coating most desired.

The features of the present invention which are believed to be novel are set forth with particularity in the appended claims. This invention itself, both as to its organization and manner of operation, together with further objects and advantages thereof, may be best understood by reference to the following description taken in connection with the accompanying drawings in which:

FIG. l shows in general form a system embodying features of the present invention.

FIG, 2 illustrates in more detail the circuitry for the flow of anodizing tank bath currents.

FIG. 3 illustrates in detail the control circuitry indicated at 99 (two places) in FIG. l.

FIG. 4 illustrates graphically on the same time scale various conditions existing in the system of FIG. l.

FIG. 5 illustrates a modified wave form used under certain conditions, produced by modification of the apparatus shown in FIG. 2.

FIG. 6 illustrates another modified form used under certain conditions.

The system is illustrated generally in FIG. 1 and involves an A.C. source 24 supplying current to an anodizing tank 10 via a transformer 28 having taps 29C, 29F and 29E on its secondary winding 29.

Tap 29C is connected to the positive terminal 15 of the anodizing tank 10 which has its metal container grounded.

Tap 29F is connected to the grounded tank via a series circuit which includes an ammeter shunt resistance 36 and a silicon controlled (SCR) rectifier 22 for the supply of negative current through the tank 10, such negative current being controlled by a control signal applied to the gate electrode of the rectifier 22. Such control signal is developed in the control unit 99A (FIG. 3) in response v to the average value of current owing through resistance 36.

Likewise, tap 29E is connected to the grounded tank via a series circuit which includes an ammeter shunt resistance 36 and a pair of parallel connected silicon controlled rectifiers (SCR) 20, 21 (FIG. 2) for the supply of positive current through the tank 10, such positive current being controlled by a control signal applied to the gate electrode of rectifiers 20, 21 jointly. Such control signal is developed in the control unit 99 (FIG. 3, two of which are provided in the complete system) in response to the average value of positive current flowing through resistor 33.

The anodizing system in FIG. 2 involves a metal tank 10 maintained at ground potential containing a liquid bath 11 Within which the part 12 is suspended using a hanger 13 supported on a cross rod 14, the rod 14 being supported on an electrical conductor 15 which in turn is supported on tank 10 using a series of electrical insulators 16. This conductor 15 provides the positive terminal of the cell and a good conductive path for the flow of heavy currents to the part 12 is assured by suitable means using, for example, clamps (not shown) to clamp the elements 14 and 15 together and also to clamp elements 13 and 14 together.

Preferably the bath is agitated using compressed air produced by either a positive displacement blower, high pressure pump or any other means known to the art which is introduced into the perforated manifold structure so that agitation is achieved by such air bubbling up through the bath which also is refrigerated using conventional refrigeration means.

Current in each of the two half cycles of an alternating current wave is controlled using a pair of silicon controlled rectifiers 20, 21 for heavy positive current iiow (during the positive half of the A..C. cycle) and one silicon controlled rectifier (SCR) for the smaller negative current flow.

The A.C. is supplied from an AC. source 24 having one of its terminals connected to the adjustable tap 26 of the primary winding 27 of transformer 28, an outside terminal of winding 27 being connected to the other terminal of source 24. The secondary winding is illustrated as having two series connected sections 29A, 29B with the adjustable tap 29C being connected to the positive cell terminal 15. An adjustable tap 291D on winding 29B is connected to an outside terminal of winding 29A and an outside terminal 29E is connected to the interconnected cathodes of rectiiiers 20, 21 through an ammeter 32 shunted by its shunt. An adjustable tap 29F on winding 29B is connected directly to the anode of rectifier 22 which has its cathode connected to the grounded tank 10 through an ammeter shunted by its shunt 36. The anodes of rectifiers 20 21 are connected to the same ground point through corresponding windings 36, 37 of a paralleling transformer 38 which functions to automatically apportion and equalize and load current between rectifiers 20, 21 in response to any unbalance in such currents. In other words, when the` currents are unbalanced a voltage is developed that tends to restore the current balance in devices 20 and 21.

A voltmeter 40 and bleeder resistor 42 may be connected across the positive and negative bus bars.

A surge or transient suppressor 44 in the general form of diodes connected in back-to-baok relationship may be connected across terminals 29C, 29E.

The gate electrode 22A of device 22 is connected to the control lead y46 through isolating resistance 48 and such lead 46 is connected to the cathode of device 22 through diode 50 for noise suppression purposes.

Likewise the gate electrodes 20A, 21A are connected through corresponding resistors 52 and 53 to the control lead 56 and a diode 58 is connected between the lead 56 and the interconnected cathodes of devices 20, 21.

Suitable signals as now described in connection with FIG. 3 are applied to the control leads 46, 56 which may be the internal conductor of a coaxial cable having its outer sheath maintained at substantially ground potential.

FIG. 3 discloses details of the control for lead 56 (FIGS. 1 and 3) but it will be understood that the following description of iFIG. 3 is applicable also to the control for the other control lead 46.

The terminals 60 and 61 in FIGS. 2 and 3 correspond to opposite terminals of the ammeter shunt 33 through which current fiows during a selected portion of the positive half wave of current. (Likewise when the lead 46 corresponds to lead 56 in the negative half Wave control amplifier then terminals 60, 61 correspond to terminals 60A, 61A which are the terminals of the ammeter shunt 36.)

Lead 61 is grounded and lead 60 is connected through a filter choke .100 to the base of transistor 102 having its emitter electrode connected to a minus 20-volt lead through resistor 108. A filter capacitor 106 is connected between such base and ground so that a filtered negative average voltage appears across capacitor 106. Such voltage is proportional to the average current flowing during the positive half cycle, i.e. through the parallel circuit comprising ammeter 32 and 500 ampere, 100 millivolt shunt 33.

This voltage is compared with a reference Voltage in the comparator circuit involving transistors 102, 110 each of which has its emitter connected through the common resistor 108 to lead -104 and which has its collector connected through a corresponding resistor 112, 114 to the positive lead 116.

lLead1116 is nominally at plus 20 volts, the same being connected to the interconnected cathodes of rectiers 120, 122 through the series connected current limiting resistance 124 and resistance 126. Lead 104 is nominally at minus 20 volts, the same being connected to the interconnected anodes of the rectifiers 130, 132 through current limiting resistor 134, and resistor 136.

A pair of A.C. sources 1140, l142 of substantially the same voltage each has one of its terminals grounded, the other terminal of source 142 being connected to the anode of device and also to the cathode of device 132. Likewise, the other terminal of source is connected to the cathode of device l130 and also to the anode of device 122.

Filter capacitors 150, 152 each have one of its terminals grounded, the other terminal of capacitor being connected to the junction point of resistances 124, 126 and the other terminal of capacitor 152 being connected to the junction point of resistances 134, 136.

A Zener diode 154 is connected between lead 116 and ground and likewise Zener diode 156 is connected between lead 104 and ground for voltage regulation purposes.

A voltage dividing circuit is connected between leads 116, 104 comprising essentially: resistors 158, 159, 160, 161 and 162 with resistor 163 shunting the outside terminals of resistor 159 to provide a fine voltage control at tap 159A on resistor 159 and a relatively coarse control at the tap 160A on resistor 160. A resistor 166 is conasa/,ssa

nected between the junction point of resistors 160, 161 and ground and a Zener diode 168i is connected between the junction point of resistors i161, 162 and ground.

Resistor tap 160A is connected to the base of transistor 110 which is in a comparator circuit, as previously mentioned, for providing a comparison between, on the one hand, an adjustable voltage established by adjustment of taps 159A, :160A and, on the other hand, an average voltage developed across capacitor 106.

The collector of transistor 102i is connected to the base of transistor 1,70 and also to one terminal of Zener diode 172 and resistor 1173` each having its other terminal connected to positive lead 116. The emitter of transistor 170 is connected to a positive lead 116 through resistor 174. The current through transistor 170 is altered for purposes explained later.

By adjustment of the tap 159g, resistance 159, the base of transistor 110 may be set Within the range of zero plus or minus 100 millivolts and this may be considered a reference voltage. In the event that the reference voltd age is greater than the average voltage developed across capacitor 106 then transistor y110 is turned on and transistor 102 is turned olf, i.e. in a nonconductive state. When transistor 102 is turned off its collector voltage rises, i.e. becomes more positive to in turn produce a smaller current iiow through transistor 1170. This results in a trigger circuit being retarded in such a way that on the next positive half cycle the silicon controlled rectifiers 20, 21 fire later to reduce the current through rectiiers 20, 21 to in turn cause the average voltage across capacitor 106 to increase to the point where the reference voltage no longer exceeds such average voltage.

For these purposes the control circuit involving transistors 176, 177 and .178 is provided. `In general, conduction of transistor 178 causes a positive voltage developed on capacitor 179 to be applied through the emitter-collector path of transistor 178 to cause the control lead `56 to become positive and the rectiiiers 20 and 211 to become conductive. This lead 56 is normally maintained at a negative potential by its connection through resistor 180 to the negative lead 104. Transistor 178 has its collector connected to control lead 56, its emitter connected to the positive ungrounded terminal of capacitor 179 and its base connected to ground -via resistor 181.

Capacitor 179 is connected in series with an A.C. source 1182, a diode 1831` and resistor '184 so as to acquire this positive charge.

The particular time at which the voltage on the precharged capacitor 179 is applied is in general determined by the condition of capacitor 186.

Capacitor 186 has one of its terminals grounded and the other one of the terminals of this capacitor 186 is connected (a) via diode 187 to the base of transistor 177, (b) to the collector of the previously mentioned transistor in the comparator network and (c) via current limiting resistor 190 to the collector of transistor 176 having its emitter electrode grounded.

The base of transistor 176 is connected to the positive lead 116 via the series connected resistors 191 and 192, such that transistor 176 would continuously conduct, but such conduction is periodically interrupted as a result of the ungrounded terminal of A.C. source 182 being connected via diode 194.` to the junction point of resistance 191 and 192. Thus transistor 176 serves as a means for shunting a current from capacitor 186 to ground. When the current flowing in transistor 170 is increased, capacitor 186 acquires in a shorter time a charge sufficient to overcome the Zener value of Zener diode 187 (which establishes a threshold) to turn on transistor 177 which has its base connected to one terminal of diode 187, its emitter connected to ground via resistor 196 and its collector connected to the positive lead 116 via the series connected resistors 198, 199 having their junction 198A point connected to the base of transistor 178. When transistor 177 conducts, transistor 178 thus also conducts causing a trigger derived from the precharged capacitor 179 to be applied to the rectifiers 20, 21 to cause them to conduct. The greater the current of transistor 170, the shorter time it takes for capacitor 186 to achieve the voltage required to cause Zener diode 187 to conduct and hence the shorter is the time before the trigger voltage is applied through transistor 178.

This procedure is graphically illustrated in FIG. 4 where the sine wave 200 represents the voltage between terminals 29C, 29E in FIGS. l and 2. In this discussion it will be understood that the A.C. source 182 has a like waveform of the same frequency. The vertical line 201 represents the time during each cycle that the rectiiiers 20, 21 are rendered conductive and the shaded area 202 represents the duration of the conduction interval. This line 201 may be adjusted in position as indicated by the double arrows 204 by adjustment of the resistance tap 160A (FIG. 3) to correspondingly increase or decrease the shaded area lwhich represents also the average current flow during the positive half of the A.C. cycle and which is monitored by the ammeter-shunt combination 32, 33 in FlG. 2. Transistor 176 is turned off, in time, at the point 206 when the effect of the D.C. voltage applied through resistance 194 (FIG. 3) is overcome when diode 1941 conducts. Transistor 176 is subsequently rendered conductive at point 208 when diode 19-1 is in a noneonductive state. ln the meantime transistors 177 and 178 are rendered conductive at the time represented by line 201.

FIG. 4(b) represents the corresponding variation in voltage across capacitor 186. When and as such voltage builds up in intensity and reaches the value represented by the horizontal line 210 (which represents the threshold voltage established by Zener diode 187) transistor 177 is turned on at point 212. This point 212 may be adjusted in time by adjustment of the resistance tap 160A to, for example, the point 213 in which case the line 201 W assumes the position of line 214.

Correspondingly the voltage across capacitor 179 is represented in FIG. 4(c) and it will be seen that such capacitor is precharged and starts discharging at the firing point 215, and again Vbecomes fully charged prior to the next firing time.

FIG. 4(d) correspondingly represents the voltage developed on the gate electrode of rectiiiers 20, 21 with respect to their cathodes. It 'will be seen that at the firing point 220 the voltage rises from a previous sustained negative value to a positive value and such voltage remains positive until point 222 is reached, point 222 corre sponding in time to the point 208 where the supply voltage wave 200 changes from a positive value to a negative value.

1t will be appreciated that FIG. 4 is useful also as an explanation of conditions associated with the negative current rectier 22 which establishes current flow during the interval indicated by the shaded area 230 in FIG. 4. The line 231 defining a boundary of such area 230 corresponds to the time of firing of the negative rectifier and the same may be controlled using a like control A in that control unit 99 associated with the negative current rectifier.

It will also be seen that by delaying or advancing the point of ring the line 231 may be shifted as indicated by the double arrow 234 to correspondingly increase or decrease the average value of negative current. The term average current in this context takes into account the fact that during a substantial portion of the negative half cycle there is no negative current flow.

New and improved results are achieved when the ratio of average negative to positive current is 3% or greater and thus preferably the apparatus previously described is so adjusted. Satisfactory operation and the production of these new results have been observed when such ratio is as high as 20%. Thus, for example, when such ratio is 3% and greater the thickness of the anodized coating may be as much as l2 mils (0.Ol2) or more and the production of a particular thickness is predictable in terms of particular values of current fiowing during particular time intervals. Further such hard coating is relatively light in color and has a great capability of absorbing dyes for permanent coloring purposes, even when coated at low temperatures as low as 15 F.; and the process also produces excellent hard coats at 40 amps per square foot even at conventional anodizing temperatures of seventy degrees Fahrenheit. Indeed satisfactory hard coats have been produced using current densities as high as 160` amperes per square foot of the part being anodized `with a bath temperature of 2'() degrees Fahrenheit.

Such hard coatings and also conventional coatings may be accomplished in a simple aqueous solution of sulfuric acid solution using higher current densities than 4() amperes per square foot with the bath maintained at such relatively high bath temperatures that refrigeration requirements are minimized, yet with the production of thick coatings in a relatively short time interval. Such coatings may be produced in aqueous solutions `where the sulfuric acid is as low as 5% and as high as 25% by volume, but we prefer to maintain the bath at Conventional anodizing can be achieved in a fraction of the usual time without impairing the quality of the coating.

Alloy 2024 and other alloys in the ZXXX series where copper content may exceed 4.5% as well as 6061 aluminum alloy which is a magnesium braced alloy. Alloys possessing large amounts of silicon (7% or greater) including diecast alloys such as 13X and 380 with silicon contents up to 13% may also be processed.

Using percentages greater than 3% the relationship between thickness of the anodized coating developed and time is a substantially linear one, i.e. the thickness produced is accurately predictable. The time required for a particular thickness is relatively small and also the coating produced has exceptionally good dielectric strength.

In those instances where it is desired to enhance the throwing power, i.e. the capability of achieving anodized coatings in shadow areas and in cavities the apparatus shown in FIG. 2 may be converted to produce the wave form involving the positive half waves 304 illustrated in FIG. 5 where it will be seen that the negative pulses are eliminated and that the positive pulses are prolonged, using capacitor means 302 (FIG. 2) such that the positive current never reaches zero or never stays at a zero value for an appreciable time interval, measured in terms of the periodicity of the A.C. wave.

This conversion may be accomplished by deactivating the negative current rectifier 20 such that it never conducts and this may be accomplished, for example, by adjustment of the tap 160A (FIG. 3) on that control unit 99 associated with the negative current such that FIG. 2 is closed to connect the large capacitor 302 between the positive terminal 15 and grounded terminal 10 of the cell, the capacitor 302 being of sufficient magnirectifier is prevented from firing. Also switch 300 in tude to sufficiently prolong the positive half waves 304 to obtain the result described above and indicated in FIG. 5 wherein the dotted line 305 illustrates the desired result of the capacitor 302.

It will be appreciated that other means than the capacitor means 302 in FIG. 2 may be used to prolong the positive pulses such that the positive current never reaches zero or never stays at a zero value for an appreciable time interval. Such other means may involve an inductor connected in series with the anodizing tank 10. Such a modification is illustrated in FIG. 6 wherein the anodizing tank l0 is connected in series with an inductor 220, such inductor 220 being connected in parallel with a switch 222 which in its closed position short-circuits the linductor to render the same ineffective. Switch 222 in its closed position has essentially the same effect as that produced when switch 300 in FIG. 2 is in its open position.

It will be appreciated that the invention is applicable not only to the use of single phase currents but also to 8 multiphase currents such as two-phase and three-phase currents. Using such multiphase currents the throwing power may be increased if desired by inserting inductance 'in series with the anodizing tank as exemplified in FIG.

6 or by inserting capacitance in parallel with the tank 10 as exemplified in FIG. 2. The same is generally true with respect to whether the rectification is of the fullwave type or of the half-wave type.

It will be further appreciated that the broader aspects of the present invention are not dependent on the particular shape of the current wave since the same may be of sine wave character, square wave character, or predominantly sharp peaks.

It will be appreciated that aspects of the present invention are applicable to so-called conventional anodizing, i.e. anodizing accomplished at temperatures above approximately 65 Fahrenheit to produce so-called clear but dyeable thin coatings of thickness of from .2 mil to .4 mil (.0002 to .0004) as well as to hard anodic coatings of appreciably larger thicknesses.

While the particular embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects and, therefore, the aim in `the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of this invention.

We claim:

1. In an anodizing system wherein it is desired to anodize aluminum and its alloys in an anodizing bath, the improvement which resides in supplying positive and negative current alternately through said bath with the ratio of average negative current to average positive current being greater than approximately three percent but less than twenty percent.

2. A system as set forth in claim 1 in which the negative current is caused to flow after a time interval after cessation of positive current flow during which time interval neither positive nor negative current flows.

3. The improvement as set forth in claim 1 wherein said bath is a sulphuric acid bath of concentration by volume in the range of 5 to 25 percent.

4. A system as set forth in claim 2 in which the positive current is caused to flow after a second time interval after cessation of negative current fiow during which second time interval neither negative nor positive current fiows.

S. A system as set forth in claim 2 in which the negative current is automatically and continuously maintained at a constant average value regardless of voltage or resistance variations in that path through which said current flows.

6. A system as set forth in claim 4 in which the positive current is automatically and continuously maintained at a constant average value regardless of voltage or resistance variations in that path through which said current Hows.

7. A system as set forth in claim 4 in which both the positive current and the negative current is automatically and continuously maintained at a constant value regardless of voltage or resistance variations in that path through which said positive and negative current fiows.

8. In an anodizing process wherein a basically aluminum part is to be anodized in an anodizing bath, the steps of supplying positive and negative currents at different times and in sequence through said bath with a ratio of average negative current to average positive current being greater than approximately three percent and less than approximately 20 percent.

9. The process as set forth in claim 8 including the step of maintaining said negative current substantially constant regardless of voltage variations across said bath.

1.0. The process as set forth in claim 8 including the step of maintaining said positive current substantially constant regardless of voltage variations across said bath.

11. The process as set forth in claim 8 in which said current remains substantially at the same high value bel@ ginning from and lasting throughout the duration of the FOREIGN PATIENTS angz tf th 1 9 l d th t 543,071 10/1957 canada 204-58 e process se or 1n c aim inc u mg e s ep of maintaining said positive current substantially constant, OTHER REFERENCES regardless of voltage variations across said bath. 5 Metal Finishing, May 1956, Page 55, WefnCk & PIIHCT- References Cited JOHN H. MACK, Primary Examiner UNITED STATES PATENTS R. L. ANDREWS, Assistant Examiner 1,735,509 11/1929 Setoh et al. 204-58 10 Us CL X R 2,951,025 8/1960 Mostovych 204-211 204 58 

